1. Field of the Invention
This invention relates to a process for growing large single crystals of alpha-aluminum orthophosphate and alpha-gallium orthophosphate.
2. Description of the Prior Art
Alpha-aluminum orthophosphate (berlinite) and alpha-gallium orthophosphate (GaPO.sub.4) are among several alpha-quartz isomorphs that have for decades been synthesized for research purposes. An attempt to grow large single crystals of berlinite began after World War II, in an effort to find new piezoelectric crystals for frequency control applications. The project ended a few years later, because success was achieved in quartz crystal growth and because quartz was considered superior for the piezoelectric devices known then. Specifically, it was concluded that berlinite has a lower Q and lower coupling coefficient than quartz. Furthermore, tests on both X and Y cuts of berlinite plates, showing a negative frequency drift with increasing temperature, indicated that there was little chance of finding a zero temperature cut similar to the AT cut of quartz.
Interest in berlinite was renewed in 1976, when Barsch and Chang found that berlinite does have temperature-compensated cuts and that the coupling coefficient for surface acoustic wave (SAW) devices can be four times greater than for quartz.
Several processes for preparing berlinite have been reported in the technical literature (W. Jahn et al., Chem. Erde 16, 75 (1953); J. M. Stanley, Ind. Eng. Chem. 46, 1684 (54); E. D. Kolb et al., J. Crystal Growth 43, 313 (1978)); and L. E. Drafall et al., RADC-TR-80-73, Final Technical Report, March, 1980.
In a typical process, seed crystals are suspended near the bottom of a vertical autoclave and nutrient powder is suspended in a basket at the top. Both seed and nutrient are immersed in concentrated phosphoric acid. In one variation of the process, the temperature is raised slowly from about 150.degree. C. over a period of days. In another variation, a temperature gradient is maintained in the autoclave. In some cases, a gradient is maintained as the temperature is slowly raised.
More recently, U.S. Pat. No. 4,382,840, issued on May 10, 1983, discloses a process and apparatus for growing metal orthophosphate crystals from seed crystals in a horizontally-oriented pressure vessel.
Although most of the processes reported involve growth in phosphoric acid, two recent reports on growth in hydrochloric acid have appeared. Detaint et al., Proc. 34th Symp. on Freq. Control, p. 93 (1980), grew berlinite crystals from powder by increasing the temperature 4.degree. C. per day during hydrothermal growth in HCl. Kolb et al., J. Crystal Growth 51, 178 (1981), achieved higher growth rates in HCl at comparable conditions to those used for H.sub.3 PO.sub.4 growth. In their method, a temperature gradient of about 1.degree.-3.degree. C. was maintained as the temperature was increased from about 150.degree. C. to about 200.degree. C. or higher at 2.degree.-20.degree. C./day.
A problem that none of the prior art has addressed is that of growing large crystals; i.e., crystals whose longest dimension is at least 150 mm. By prior art processes, growing such large crystals, which are desirable for commercial production of berlinite, would require excessively long periods of time.